Red dye and process of making same.



'nnrr RUDOLF PUMMERER, OF LUDWIGSHAl EN-ON-THE-RH1NE, GERMANY, ASSIGNOR TO BADISGHE ANIL1N'& SODA FABRIK, 01* l1UDWIGSllAFEN-ON-TllE-ltHINE, GER- MANY, A CORPORATION OF GERMANY.

RED DYE AND PROCESS OF MAKIN G SAME.

Specification of Letters Patent.

Patented Jan. 14, 1 908.

nmion fil d September 14,1907. Serial No. 392.839.

To all whom it may concern:

Be it known that I, RUDOLF PUMMERER, doctor of philosophy and chemist, subject of the King. of Bavaria, residing at Ludwig shafenonthe --Rhine, Gern'iany, have in vented new and useful Improvements in Red Dyes and Processes of Making the Same, of

which the following is a specification.

I have discovered that 2.3diketo-dihydro (1)-thionaphthene @7 9 l6 l ZlJOr \s and its homologues and derivatives can be made to react with 1ndoxyl, orwith-S eig- (1) thionaphthene (formerly termed th1o1ndoxyl),

l o (l n or with homologues and derivatives of these compounds and that thereby new coloring matters can be obtained which dye cotton, from a hydrosulfite vat, yielding shades which vary from blue to red according to the compounds GIIlPlOYGd. The reaction can be carried out by heating the said compounds together with orwithout, the presence of diluting agents, such for instance as naphthalene, nitrobenzene, and ainylalc'ohol, and with, or without, the addition of a condensing agent, such. for instance acetic anhy .lrid, zinc chlorid, calciu1n chlorid and, in particular, mineral acids. Instead of the 3oxy- (1).thionaph-thene compounds, the correspondin arylthioglycollic acids, orthe orthocar'oxyl derivatives thereof, can be em loyed. The coloring matters obtainable as ereinbel'ore described can also be converted, by means oi'sull'onating agents, into their sulfonic acids which dye animal fiber from an acid bath, yielding blue-violet to brown-red shades.

My new coloring matters possess the following generic properties. They consist, when dry, of from violet to brownish red powders, they are soluble in benzene yielding from violet to yellowish red solutions, and in' form of their sulfoacids they die wool from blue-violet to brown-red shades.

The new coloring'matter which I desire to claim specifically is that obtainable by acting on 2.3-diketodil1ydro-(1 )thiona1 hthene with 3-oxy-(1)-thionaphthene and it consists of a red powder which gives a yellowish red solution in benzene and an olive-brown solution in concentrated sulfuric acid. It dyes cotton from an alkaline hydrosulfite vat scarlet-red shades, and in its sulfonated form dyes WOOl' red.

The following examples will serve to illustrate further the nature of my invention, which, however, is not confined to these examples. The parts are by weight.

-Example 1. Melt together, for one (1) hour, at a temperature of one hundred and forty (140) degrees centigrade (While excludmg air), one hundred and sixty-four (164) parts of 2.3-diketo-dihydro-(1)-thionaphthene and 150 parts of 3oxy(1)thionaphthene. When the melt is cold, powder'it and by treatment with hydrosulfite, or with sodium sulfid solution, purify the red. coloring matter obtained.

Example 2. Pour together solutions of one hundred and sixty-four (164) parts of 2.3-

diketo-dihydro-(I)-thionaphthene and one hundred and fifty 150) parts of 3-oxy-(1 thionaphthene each in seven hundred (700) parts of boiling acetic anhydrid, and boil the whole for thirty (80) minutes in a reflux apparatus. Then pour it into ten thousand (10,000) parts of boilingdilute acetic acid and filter off and wash, with hot water, the coloring matter which separates out and which is identical with that obtained according to the foregoing Example 1.

Instead of 3-oxy-(1)thionaphthene in the foregoing examples, the corresponding quantity of 3-oxy-(1)-thionaphthene-2-carboxylic acid can be employed;

Example 3. Boil together for one(1) hour in a reflux apparatus, while excluding air, one hundred and sixty-four parts (164) of 2.IS-diketo-dihydro-(1)-thionaphthene, one hundred and thirty-three '(133) parts of indoxyl and one thousand (1,000) parts of amylalcol'iol, then distil oil the greater part of the an'iylalcohol, stir the residue with benzene and filter off the coloringmatter which dyes cotton from the vat blue-violet shades. In this example, instead of indoxyl,

the corresponding quantity of indoxylic acid can be used.

"Example 4. Dissolye one hundred and seventy-mne (179) parts of 2.3 di'keto-d ihy dro-(l)-thionaphthene-2-oxim i I --co d=uon in the necessary quantity of boiling water,

which preferably contains some acetic acid,

, add an aqueous solution of one hundred and thirty-three (133) parts of indoxyl and three thousand (3,000) parts of concentrated h drochloric acid, boil the whole, and filter. 0 and wash, with hot water, the coloring matter whlch'dyes cotton, from the vat, blue shades.

Exam le f5. Dissolve carefully one (1) art of t e coloring matter obtained according to the foregoing Example 4 in ten (10) parts of concentrated sulfuric acid, or in two (2) parts of twenty-three (23) per cent. oljeum, and allow thersolution to stand at ordinary temperature until a test portion yields a clear solution in water. Then pour the reaction mixture into fifty parts of ice-cold concentrated salt solution and filter off and wash, with salt solution, the sulfonic acid which separates out. I

Example 6. Boil together for two (2) hours in a reflux apparatus, two hundred and twelve (212) parts of ortho-carboxy' phenyl-thioglycollic acid, one hundred and sixty-four (1645) parts of 2.3-diketb-dihydro- (1)-thionaphthene, two thousand (2,000) parts of acetic anhydrid and forty (40) parts of anhydrous sodium'acetate. Then pour the. reaction li uid into ten thousand (10,000) partstof oiling water and filter off and wash, with hot water, the coloring matter which separates out n, red flakes.

In a similar manner to those described in the above examples, coloring matters can'be obtained from 5-chlor-2.3-diketo-dihydro- (1 )-thionaphthene -2 -oxim thionaphthene CH3/\--CO dihydro- (1 )thionaphthene.

Now. what I claim is:

1. The process of producing coloring mat ter by acting on a 2.3-diketo-dihydro-(Q thionaphthene compound, with an indoxyl c compound.

. 2. The process of producing coloring miitr by acting on 2.3diketo-dihydr -(1) thf naphthene with 3-oxy(l)-thi onaphene.

3. The process of producin coloring matnaphthene with 3-oxy-(1)-thionaphthene in the presence of a condensing agent.-

I'o ter by acting on2.3-diketo-di ydro-(l) thiov4. As new articles of manufacture the coloring matters which can be obtained by acting' on a 2.3-diketo-dihydro(1) thionaph- .thene compound with an -indoxylic compound, which coloring matters consist when dry of from violet to brownish red powders and are soluble inbenzene yielding from. violet toyellowish red solutions and in concentrated sulfuric acid yielding from brown to green solutions and are soluble in alkaline hydrosulfite I I from blue to red shades, and in the form of their sulfoacid dye cotton from blue-violet to brown-red shades.'

yielding vats which dye cotton x -MKHM/M 5. As a new article of manufacture the f coloring matter which can be obtained by acting on 2.3-diketo-dihydro-(1 )thionaphthene with 3-oxy-(1)tl1ionaphthene, which coloring matter consists when dry of a red owder and gives a yellowish red solution in benzene and an olive-brown solut on in concentrated sulfuric acid, and dyes cotton from an alkaline hydrosulfite vat scarlet-red.

shades and in its sulfonated form dyes wool red.

Intestimony whereof I have hereunto set my hand in-the presence of two subscribing witnesses.

RUDOLF PUMMERER.

Witnesses:

J. Auto. LLOYD, Jos. H. LEUTE. 

